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Ferrandin-Schoffel Et Al Manus Modeling the Reactivity of Aged Paper with Aminoalkylalkoxysilanes as Strengthening and Deacidification Agents Nathan Ferrandin-Schoffel, Mohamed Haouas, Charlotte Martineau-Corcos, Odile Fichet, Anne-Laurence Dupont To cite this version: Nathan Ferrandin-Schoffel, Mohamed Haouas, Charlotte Martineau-Corcos, Odile Fichet, Anne- Laurence Dupont. Modeling the Reactivity of Aged Paper with Aminoalkylalkoxysilanes as Strength- ening and Deacidification Agents. ACS Applied Polymer Materials, American Chemical Society, 2020, 2 (5), pp.1943-1953. 10.1021/acsapm.0c00132. hal-02887844v2 HAL Id: hal-02887844 https://hal.archives-ouvertes.fr/hal-02887844v2 Submitted on 27 Nov 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Modeling the reactivity of aged paper with aminoalkylalkoxysilanes as strengthening and deacidification agents Nathan Ferrandin-Schoffel1,2*, Mohamed Haouas3, Charlotte Martineau-Corcos3, Odile Fichet2, Anne- Laurence Dupont1* 1Centre de Recherche sur la Conservation des Collections (CRC, CNRS USR 3224), Muséum National d'Histoire Naturelle, 36 rue Geoffroy St Hilaire 75005 Paris, France 2Laboratoire de Physicochimie des Polymères et des Interfaces (LPPI, EA 2528), Institut des Matériaux, Université de Cergy-Pontoise, 5 mail Gay-Lussac, Neuville sur Oise, 95031 Cergy-Pontoise cedex, France 3Institut Lavoisier de Versailles (ILV, UMR 8180), Université de Versailles Saint-Quentin, 45 avenue des Etats- Unis, 78035 Versailles, France *Corresponding authors: [email protected], [email protected] Keywords Aminoalkylalkoxysilane - Cellulose - Lignin - Modelling - Nuclear magnetic resonance - Schiff base Abstract Aminoalkylalkoxysilane (AAAS) flexible copolymer networks can be used to deacidify and strengthen paper in a one-step operation. The treatment is versatile and can be tailored to convey a balanced combination of tensile strength and pliability to degraded paper from library and archives collections. The treatment efficiency on bleached pulp and rag or cotton paper has been shown to be always suitable. It is however challenged when the paper contains lignin and is very degraded. The reasons for this are still poorly understood. Indeed, the reactions at room temperature of AAAS with the biopolymers in paper are difficult to characterize. In this work, the hydrolysis and polycondensation reactions of an AAAS monomer (3-aminopropylmethyldiethoxysilane, AM) were closely examined, and the interactions with lignin and cellulose were studied using a modelling approach. To this end, several model organic molecules were used to reproduce the main functional groups of cellulose and lignin. The reactions with AM were studied with ATR-FTIR and NMR using 1H, 13C, 29Si, and 1H-X (X = 13C, 15N, or 29Si) heteronuclear multiple bond correlation (HMBC). The results showed that carbonyl and carboxyl groups react with the amine and silicate moieties of AM. These results are paralleled with the physico- chemical properties of three oxidized and brittle newsprint papers to explain the variable degree of strengthening observed upon AAAS treatment. A Supplementary Material file is available. It contains supporting information to the article, including ATR-FTIR spectra (J1, J2 and J3, vanillin and AM/vanillin, vanillic acid and AM/vanillic acid, p- benzoquinone and AM/p-benzoquinone), 13C NMR spectra (AM, methyl-β-D-glucopyranoside (MGPO), and AM/MGPO) and 1H NMR spectra (p-benzoquinone and AM/p-benzoquinone). 1 1. Introduction Paper slowly decays with time. Cellulose, the main biopolymer in paper, undergoes acid-catalyzed hydrolysis that decreases the degree of polymerization (DP), which in turn progressively leads to loss in mechanical resistance of the paper. In addition, the natural slow formation of carbonyl compounds among other degradation by-products increases the acidity. Late 19th - early 20th century lignocellulosic paper collections, especially newsprint paper of mediocre quality, degrade faster than more durable paper, and can become extremely brittle. As a preventive measure, mass treatments have been developed for the deacidification of libraries and archives collections.1–4 Nevertheless, these processes do not provide a comprehensive solution for the most degraded (acidic and brittle) documents, which additionally, would need to be mechanically strengthened. In order to overcome this problem, one-pot treatments based on the use of aminoalkylalkoxysilanes (AAAS), imparting simultaneous deacidification and strengthening to cellulosic objects, have been proposed.5–11 Previously published results showed the full potential of AAAS treatments in organic solvent phase, including fungistatic properties of the treated documents.12 At the laboratory or the conservation workshop scale, the treatment can be applied by spray or by immersion, undiluted or diluted in an organic solvent, usually hexamethyldisiloxane (HMDSO). At the ‘’mass’’ industrial scale, the use of a non- protic solvent such as HMDSO is recommended to avoid the bleeding of water-soluble inks, dyes and binders, fiber swelling, and also to shorten the drying time.1,8,13 More recently, flexible copolymer networks (co-AAAS) have been studied, with the aim of conveying a balanced combination of tensile strength and pliability to very degraded paper.11 The treatment is versatile as its formulation can easily be modified by changing the monomers, their proportions and their concentration. Efficient deacidification and increase in the tensile breaking length has been obtained,11,14 but an increase in folding endurance increase was less easily achieved,14,15 and slight yellowing was sometimes observed.9,10 The interactions taking place between the AAAS and the paper are still unclear. The aim of this research was thus to investigate these interactions. It has been previously suggested that the amine group, which drives the deacidification, also favors the adsorption of the AAAS in the cellulosic material and forms hydrogen bonds.8–10 To account for the observed slight yellowing of the treated papers, the formation of Schiff bases through covalent bonding between the amine groups and carbonyl groups in oxidized paper was hypothethised.5,6,9,10 On the other hand, strengthening, which is thought to be imparted by the in situ polymerization, thus depends on the DP of the AAAS, i.e. on their ability to hydrolyze with the water naturally absorbed in the fibers in the first step of the reaction (eq. 1), and to subsequently condensate at room temperature. The condensation step can be hydrolytically-driven (eq. 2) in which case water is regenerated16 or alcohol-driven (eq. 3). 2 Hydrolysis: H O Si OH + ROH Si OR + 2 (eq. 1) Hydrolytic polycondensation: + OH Si Si O Si +H O (eq. 2) Si OH 2 Alcoholic polycondensation: Si OH + RO Si Si O Si + ROH (eq. 3) In acidic conditions and at room temperature the hydrolysis of alkoxysilanes is catalyzed, whereas the condensation is slower and can take up to several months.17,18 In contrast, it has been shown that both the hydrolysis and the polycondensation steps are catalyzed in alkaline conditions.17–19 Hence, these reactions can be catalyzed by the amine functions on the AAAS molecules.18,19 Acids continuously produced during the natural aging of paper would partly neutralize these bases in situ, gradually leading to near-neutral conditions and subsequently slower polycondensation kinetics. Likewise, the proposed formation of covalent bonds between the amines of the AAAS and carbonyl groups from the degraded paper could in all likelihood limit the size of the polymer. As another induced drawback, the alkaline reserve brought by the amine group would be lower than expected. Previously, it has been suggested that several constituents of the paper were likely to affect the treatment’s efficiency. Among them, alum-rosin sizing14,15 and groundwood pulp,10,15 which are present in significant amount in early newsprint paper made from unpurified wood. Mechanical pulp from softwood typically contains between 25 and 31 wt% of lignin in the near-native form.20 Lignin is an amorphous tridimensional biopolymer largely responsible for the paper acidity and yellowing upon aging.21 More generally, reactions that occur at room temperature in the paper between AAAS and the biomacromolecules, i.e. cellulose, hemicelluloses and lignin, are difficult to characterize and are still not fully understood. For example, most routine spectroscopic techniques do not have enough resolving power to characterize precisely carbonyl groups in-situ.22 In this work, we identified possible reactions taking place between the AAAS and the paper, which could explain the variable degree of strengthening obtained with different papers. To this purpose, a model study was undertaken. Several organic molecules were chosen as their structure encompassed the main functional groups of cellulose and lignin. They were mixed to 3-aminopropylmethyldiethoxysilane, henceforth called AM, a bifunctional AAAS that condensates into a linear polysiloxane. Fourier-transform infrared
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